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Simultaneous absorption of UV-vis and circular dichroism to measure enantiomeric concentrations of praziquantel under nonlinear conditions.
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy ( IF 4.3 ) Pub Date : 2020-07-03 , DOI: 10.1016/j.saa.2020.118645
F C Cunha 1 , R C de Holanda 2 , A R Secchi 3 , M B de Souza 3 , A G Barreto 2
Affiliation  

Beer-Lambert-Bouguer law is for a limiting case and, therefore, it is not useful to describe the relationship between absorption signal and enantiomer concentration in a stream when there are nonlinear phenomena present. In this work, the Chiral Detector (CD-2095 JASCO) equipment was used to measure simultaneously the UV–Vis and circular dichroism (CD) signals of a stream with different compositions of praziquantel enantiomers. The tested models were calibrated (parameter estimation) and validated using the Leave-One-Out Cross Validation (LOOCV) method. Both UV–vis and CD signals were absorbed differently in mixtures in comparison to pure solutions, indicating a nonlinear relationship between the absorbed signal and the enantiomer concentration in a mixture stream. Empirical mathematical relationships were tested for each signal (UV–vis and CD) and the pair of equations was evaluated using the Mean Square Error (MSE) metric for each enantiomer concentration (MSEL and MSED) and the pair of equations with the smallest MSEt (=MSEL + MSED) metric was chosen. Confidence interval analysis helped to find even simpler equations in comparison to the chosen ones. Higher nonlinearity was observed for a mixture with low L-PZQ concentration. The developed methodology allowed the choice of an empiric model to give good predictions in a wide range of concentration, what is of utmost importance for monitoring and automatic control purposes, for instance.



中文翻译:

同时测量紫外可见光和圆二色性,以测量非线性条件下吡喹酮的对映体浓度。

Beer-Lambert-Bouguer定律是一个极限情况,因此,当存在非线性现象时,描述流中吸收信号与对映异构体浓度之间的关系是无用的。在这项工作中,手性检测器(CD-2095 JASCO)设备用于同时测量具有不同吡喹酮对映体组成的物流的UV-Vis和圆二色性(CD)信号。所测试的模型进行校准(参数估计)和验证使用大号eave- ø NE- ö UT Ç罗斯V滑动法(LOOCV)。与纯溶液相比,UV-vis和CD信号在混合物中的吸收不同,这表明混合物流中吸收的信号与对映异构体浓度之间存在非线性关系。经验数学关系进行了为每个信号(UV-vis和CD)和一对方程的测试使用评价中号EAN小号quare ë RROR(MSE)为每个对映异构体的浓度(MSE度量大号和MSE d)和一对方程MSE t(= MSE L  + MSE D)指标。置信区间分析有助于找到比所选方程更简单的方程。L-PZQ浓度低的混合物观察到较高的非线性。所开发的方法允许选择经验模型以在广泛的浓度范围内给出良好的预测,例如,对于监视和自动控制而言,这是最重要的。

更新日期:2020-07-08
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